CN111909695B - Rare earth up-conversion and perovskite quantum dot composite nanomaterial and preparation method and application thereof - Google Patents
Rare earth up-conversion and perovskite quantum dot composite nanomaterial and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a rare earth up-conversion and perovskite quantum dot composite nano material and a preparation method and application thereof. A simple two-step epitaxial growth method is developed to prepare the composite nano material, and the prepared composite nano material has good dispersibility, uniformity and repeatability; under the excitation of a low-power density 980nm continuous semiconductor laser, due to CaF2Ln nanocrystal and CsPbX3The quantum dots have an efficient fluorescence resonance energy transfer process, so that CsPbX in the composite nano material is realized3The up-conversion luminescence of the quantum dots has the energy transfer efficiency as high as 99.7 percent; due to CaF2Ln nanocrystal pair CsPbX3Protection of quantum dots, and compared with pure CsPbX, the composite nano material3Quantum dots, CaF2Ln nanocrystals and CsPbX3The quantum dot physical mixed material has stronger down-conversion fluorescence emission, better thermal stability and air stability. Therefore, the composite nano material can be used as an up-conversion and down-conversion dual-mode luminescent material, and has potential application prospects in the fields of photoelectricity, photovoltaic devices and the like.
Description
Technical Field
The invention belongs to the technical field of nano luminescent materials, and particularly relates to a rare earth up-conversion and perovskite quantum dot composite nano material, and a preparation method and application thereof.
Background
The rare earth up-conversion nano luminescent material has weak background interference and long fluorescence lifeThe advantages of long service life, low excitation energy, deep tissue penetration and the like, thereby showing wide application prospects in the fields of illumination display, drug transportation, biomedical imaging, biomarkers and the like, and being a research hotspot at home and abroad in recent years. The perovskite quantum dots are of a type related to calcium titanate (CaTiO)3) Materials with the same crystal structure are mainly divided into organic-inorganic hybrid and all-inorganic trihaloperovskite. The organic-inorganic hybrid perovskite has great success in photovoltaic devices, and the stability of the all-inorganic trihalogen perovskite is superior to that of the organic-inorganic hybrid perovskite, so that the organic-inorganic hybrid perovskite has great research significance and good application prospect. The full inorganic perovskite quantum dot has the advantages of extremely high fluorescence quantum efficiency, adjustable fluorescence wavelength, coverage of the whole visible light wave band, narrow line width, good electric transmission characteristic and the like, so that the full inorganic perovskite quantum dot has great application prospects in the fields of luminous display, photoelectric conversion, detection and the like, such as solar cells, lasers and light emitting diodes.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a rare earth up-conversion and perovskite quantum dot composite nanomaterial, and a preparation method and application thereof. The invention designs a rare earth up-conversion and perovskite quantum dot composite nanomaterial based on the excellent optical properties of both rare earth up-conversion nanomaterials and all-inorganic perovskite quantum dots. Under the excitation of infrared light, rare earth up-conversion nano material and all-inorganic perovskite quantum dot (namely, full series CsPbX)3Quantum dots), and the efficiency of fluorescence resonance energy transfer between the rare earth up-conversion nano material and the perovskite quantum is as high as more than 99.7%, so that near infrared light which cannot be utilized by the silicon-based solar cell can be effectively utilized, and the purpose of fully utilizing solar energy is achieved. Meanwhile, due to the protection effect of the rare earth up-conversion nano material on the all-inorganic perovskite quantum dot, compared with the all-inorganic perovskite quantum dot, the composite nano material has better stability (such as air stability and thermal cycle stability) and better down-conversion fluorescence property (the down-conversion fluorescence intensity and the quantum yield are improved). Thus, development of such a rare earth upconversionAnd the perovskite quantum dot composite nano material has important practical significance and value in the application of photoelectric and photovoltaic devices.
The purpose of the invention is realized by the following technical scheme:
a rare earth up-conversion and perovskite quantum dot composite nanomaterial, the composite nanomaterial comprising up-conversion nanoparticles and perovskite quantum dots, the up-conversion nanoparticles having a chemical formula of: CaF2Ln, wherein Ln is Yb3+/Er3+And Yb3+/Tm3+(ii) a The perovskite quantum dot is CsPbX3And the quantum dots are characterized in that X is selected from one of Cl, Br and I.
According to the invention, the chemical formula of the rare earth up-conversion and perovskite quantum dot composite nano material is CsPbX3/CaF2Ln. Illustratively, the rare earth up-conversion and perovskite quantum dot composite nanomaterial has a chemical formula of CsPbCl3/CaF2:Yb,Tm、CsPbBr3/CaF2:Yb,Tm、CsPbI3/CaF2:Yb,Tm、CsPbCl3/CaF2:Yb,Er、CsPbBr3/CaF2Yb, Er and CsPbI3/CaF2Yb, Er; preferably, the chemical formula of the rare earth up-conversion and perovskite quantum dot composite nano material is CsPbCl3/CaF2:Yb,Tm、CsPbBr3/CaF2Yb, Tm and CsPbI3/CaF2:Yb,Er。
According to the invention, the upconversion nanoparticles and the perovskite quantum dots are connected through chemical bonding. The up-conversion nano particles and the perovskite quantum dots are combined at an atomic scale, and the up-conversion nano particles are embedded in the perovskite quantum dots and are bonded and connected through chemical bonds.
According to the invention, the molar ratio of Yb to Tm is (5-40): 0.5-2, preferably (9-36): 0.8-1.2, for example 36: 1; the molar ratio of Yb to Er is (5-40): (0.5-2), preferably (9-36): 0.8-1.2, for example 36: 1.
According to the present invention, the crystal system of the upconversion nanoparticles is not particularly limited, and may be, for example, a cubic phase calcium fluoride nanocrystalline structure.
According to the present invention, the crystal system of the perovskite quantum dot is not particularly limited, and may be, for example, a cubic phase structure.
Preferably, when the up-conversion nanoparticles and the perovskite quantum dots are both selected from a cubic crystal system, the combination of the up-conversion nanoparticles and the perovskite quantum dots on an atomic scale is more favorable, and when the up-conversion nanoparticles and the perovskite quantum dots are selected from other crystal systems, the composite nano material can be prepared.
According to the invention, the particle size of the up-conversion nanoparticles is 1-10 nm, preferably 2-5 nm, and further preferably 3-4 nm.
According to the invention, the CsPbX3The particle size of the quantum dots is 5-50 nm, preferably 10-40 nm, and further preferably 20-30 nm.
According to the invention, in the rare earth up-conversion and perovskite quantum dot composite nano material, the molar ratio of perovskite quantum dots to up-conversion nano particles is (3-6): (0.5-2), preferably (4.5-5.5): (0.5-1.5).
According to the invention, the particle size of the rare earth up-conversion and perovskite quantum dot composite nano material is 1-50 nm, preferably 10-50 nm, and further preferably 20-40 nm.
The invention also provides a preparation method of the rare earth up-conversion and perovskite quantum dot composite nano material, which comprises the following steps:
(1) preparing an upconversion nanoparticle having the formula: CaF2Ln, wherein Ln is Yb3+/Er3+And Yb3+/Tm3+；
(2) And preparing the rare earth up-conversion nano particles and the perovskite quantum dot composite nano material.
According to the invention, the upconversion nanoparticles are prepared by a coprecipitation method. Illustratively, the upconversion nanoparticles are prepared by a method comprising:
(1-1) mixing a calcium source and an Ln source and dissolving into oleic acid and octadecene to obtain a mixed system A, wherein Ln is Yb3+/Er3+And Yb3+/Tm3+；
(1-2) mixing ammonium fluoride, sodium hydroxide and methanol to obtain a mixed system B;
(1-3) mixing the mixed system A obtained in the step (1-1) with the mixed system B obtained in the step (1-2), and reacting to prepare the up-conversion nanoparticles, wherein the up-conversion nanoparticles have a chemical formula: CaF2Ln, wherein Ln is Yb3+/Er3+And Yb3+/Tm3+。
According to the invention, in the step (1), the upconversion nanoparticles are cubic-phase CaF2Ln nanocrystals.
According to the present invention, in the step (1-1), the calcium source may be calcium acetate, for example, calcium acetate monohydrate; the Ln source may be ytterbium acetate and erbium acetate, or ytterbium acetate and thulium acetate, such as ytterbium acetate tetrahydrate, erbium acetate tetrahydrate, or thulium acetate tetrahydrate.
According to the invention, in the step (1-1), the molar ratio of the calcium source to the Ln source is (0.5-0.95): (0.046-0.41), preferably (0.78-0.89): (0.1004-0.2006). Illustratively, the molar ratio of calcium acetate, ytterbium acetate, erbium acetate or thulium acetate is (0.5-0.95): (0.045-0.4): 0.001-0.01), preferably (0.78-0.89): 0.1-0.2): 0.004-0.006.
According to the invention, in the step (1-1), the volume ratio of oleic acid to octadecene is (1-10): 10-20, preferably (3-6): 14-16.
According to the invention, in the step (1-1), the molar volume ratio of the calcium source to the oleic acid in the mixed system A is (0.5-0.95 mmol): 1-10 ml, preferably (0.78-0.89 mmol): 3-6 ml.
According to the invention, in the step (1-1), the mixing and dissolving are carried out by heating to 140-180 ℃ under an inert atmosphere, stirring for 0.2-1 hour, and preferably, the process further comprises cooling to room temperature.
According to the invention, in the step (1-2), the molar ratio of ammonium fluoride to sodium hydroxide is (1-5): 1-5, preferably (2-3): 2-3. The molar volume ratio of the ammonium fluoride to the methanol is 0.1 to 0.5mmol/mL, preferably 0.2 to 0.3 mmol/mL.
According to the invention, in the step (1-3), the volume ratio of the mixed system A to the mixed system B is (1-5): 1, for example (2-3): 1 is, for example, 2: 1.
According to the present invention, in the step (1-3), it is preferable that the mixed system B is added to the mixed system A. The mixing is carried out by heating to 70-90 ℃ under inert atmosphere, and stirring until methanol in the system is exhausted, for example, stirring for 0.5-0.8 hour.
According to the invention, in the step (1-3), the reaction is carried out by heating to 260-300 ℃ under an inert atmosphere for 0.2-1 hour.
According to the invention, the step (1) specifically comprises the following steps:
weighing calcium acetate monohydrate, ytterbium acetate tetrahydrate, erbium acetate tetrahydrate or thulium acetate tetrahydrate into a reaction container at room temperature, adding a mixed solvent of oleic acid and octadecene, heating to 140-180 ℃ under an inert atmosphere, stirring and dissolving the acetate solution for 0.2-1 hour, and cooling to room temperature; weighing ammonium fluoride and sodium hydroxide at room temperature, adding the ammonium fluoride and sodium hydroxide into methanol, adding the solution into the acetate solution, heating to 70-90 ℃ under an inert atmosphere, and stirring for 0.5-0.8 hour to drain methanol. Heating the reaction solution to 260-300 ℃ in an inert atmosphere, reacting for 0.2-1 hour, naturally cooling to room temperature, precipitating and washing to obtain cubic phase CaF2Ln nanocrystals.
According to the invention, said step (2) comprises the steps of:
(2-1) mixing and reacting cesium carbonate, oleic acid and octadecene to obtain a cesium oleate solution;
(2-2) mixing lead halide, oleic acid, oleylamine and octadecene to obtain a lead halide solution;
(2-3) mixing and reacting the up-conversion nano particles, the cesium oleate solution and the lead halide solution to prepare the composite nano material.
According to the present invention, in the step (2-1),
the mixing is carried out under the conditions of inert atmosphere and stirring, the mixing temperature is 100-130 ℃, and the mixing time is 0.8-1.2 hours.
The reaction is carried out under the conditions of inert atmosphere and stirring, the reaction temperature is 140-160 ℃, and the reaction time is 8-15 minutes.
The mass-to-volume ratio of the cesium carbonate to the oleic acid is (0.3-0.7 g): 1-2 mL, for example (0.4-0.5 g): 1.5-1.8 mL), for example 0.4g:1.5 mL. The volume ratio of the oleic acid to the octadecene is (1-5): 10-20, preferably (1-2): 14-16.
Preferably, the prepared cesium oleate solution is stored at the temperature of 100-130 ℃.
According to the present invention, in the step (2-2),
the mixing is carried out under the conditions of inert atmosphere and stirring, the mixing temperature is 100-130 ℃, and the mixing time is 0.8-1.2 hours.
The lead halide is at least one selected from the group consisting of lead chloride, lead bromide and lead iodide.
The molar volume ratio of the lead halide to the oleic acid is (0.15-0.2 mmol): 0.5-2ml), for example (0.18-0.19 mmol): 0.5-1.5ml), such as 0.188mmol:1 ml. The volume ratio of the oleic acid to the oleylamine to the octadecene is (0.5-2): 1-5): 5-15, preferably (0.5-1.5): 1-2): 8-12.
According to the present invention, in the step (2-3),
the mixing is carried out under the conditions of inert atmosphere and stirring, the mixing temperature is 100-130 ℃, and the mixing time is 0.8-1.2 hours.
The mixing is preferably carried out by mixing the up-conversion nanoparticles with a lead halide solution, then heating, adding a cesium oleate solution, and reacting in a static state.
The upconversion nanoparticles can be directly mixed with a lead halide solution, or can be prepared into an upconversion nanoparticle dispersion liquid and then mixed with the lead halide solution.
The preparation process comprises the following steps: dispersing the upconversion nanoparticles in oleic acid and octadecene to obtain a dispersion liquid of the upconversion nanoparticles; the dispersion is carried out under the conditions of inert atmosphere and stirring, the dispersion temperature is 160-200 ℃, and the dispersion time is 5-15 minutes.
The volume ratio of the oleic acid to the octadecene is (0.2-1): 2-10, preferably (0.4-0.6): 4-6); the molar volume ratio of the upconversion nanoparticles to oleic acid is (0.15-1.5 mmol): 0.5-2ml), for example (0.25-0.75 mmol): 0.5-1.5ml, such as 0.5mmol:1 ml. In order to better realize the dispersion, ultrasonic treatment can be carried out, and the ultrasonic treatment time can be 3-10 minutes, for example.
Preferably, the prepared up-conversion nanoparticle dispersion liquid is stored at the temperature of 100-130 ℃.
The reaction is carried out under the condition of inert atmosphere, the reaction temperature is 140-160 ℃, and the reaction time is 30-50 seconds.
After the reaction is finished, the reaction solution is preferably rapidly cooled to room temperature in an ice water bath, and is preferably subjected to centrifugal separation to obtain the composite nano material.
The mass-to-volume ratio of the up-conversion nanoparticles to the cesium oleate solution to the lead halide solution is (0.02-0.03 g) - (0.35-0.45 mL) - (12-13 mL), and the mass-to-volume ratio is, for example, 0.026g:0.4mL:12.5 mL.
Exemplarily, the step (2) includes the steps of:
first, CaF is reacted at room temperature2Dispersing Ln nanocrystals in a mixed solvent of oleic acid and octadecene, and performing ultrasonic oscillation for 3-10 minutes to obtain CaF2Ln nanocrystal dispersion; mixing CaF2Heating Ln nanocrystal dispersion to 160-200 ℃ in an inert atmosphere, cooling to 100-130 ℃ after 5-15 minutes, and storing;
secondly, adding cesium carbonate into a mixed solvent of oleic acid and octadecene at room temperature to obtain a cesium carbonate solution, heating to 100-130 ℃ under an inert atmosphere, and stirring and dissolving the cesium carbonate solution for 0.8-1.2 hours; heating to 140-160 ℃ so that cesium carbonate and oleic acid can completely react to obtain a cesium oleate solution, and cooling to 100-130 ℃ for storage after 8-15 minutes;
thirdly, adding lead halide into a mixed solvent of oleic acid, oleylamine and octadecene at room temperature to obtain a lead halide solution, heating to 100-130 ℃ under an inert atmosphere,stirring and dissolving the lead halide solution for 0.8-1.2 hours; mixing CaF2Drop-by-drop adding Ln nanocrystalline dispersion into lead halide solution to obtain mixed solution; keeping the mixed solution at 100-130 ℃, slowly stirring for 0.8-1.2 hours in an inert atmosphere, heating to 140-160 ℃, quickly adding cesium oleate solution, reacting for 30-50 seconds in a static state, quickly cooling the reaction solution to room temperature in an ice water bath, and centrifuging to obtain CsPbX3/CaF2Ln composite nano-material.
The invention also provides the rare earth up-conversion and perovskite quantum dot composite nanomaterial prepared by the preparation method of the rare earth up-conversion and perovskite quantum dot composite nanomaterial.
The invention also provides the application of the rare earth up-conversion and perovskite quantum dot composite nano material, which can be used as an up-conversion and down-conversion dual-mode luminescent material; it can also be used in the fields of photoelectricity and photovoltaic devices.
In the present invention, Yb is as described above3+/Er3+The meaning of which is that they contain Yb together3+And Er3+And the molar ratio of the two is not particularly limited, and may be, for example, 36: 1; yb of3+/Tm3+The meaning of which is that they contain Yb together3+And Tm3+And the molar ratio of the two is not particularly limited, and may be, for example, 36: 1.
The invention has the beneficial effects that:
the invention provides a rare earth up-conversion and perovskite quantum dot composite nano material and a preparation method and application thereof. A simple two-step epitaxial growth method is developed to prepare the composite nano material, and the prepared composite nano material has good dispersibility, uniformity and repeatability; under the excitation of a low-power density 980nm continuous semiconductor laser, due to CaF2Ln nanocrystal and CsPbX3The quantum dots have an efficient fluorescence resonance energy transfer process, so that CsPbX in the composite nano material is realized3The up-conversion luminescence of the quantum dots has the energy transfer efficiency as high as 99.7 percent; due to CaF2Ln nanocrystal pair CsPbX3Protection of quantum dots, and compared with pure CsPbX, the composite nano material3Quantum dots, CaF2Ln nanocrystals and CsPbX3The quantum dot physical mixed material has stronger down-conversion fluorescence emission, better thermal stability and air stability. Therefore, the composite nano material can be used as an up-conversion and down-conversion dual-mode luminescent material, and has potential application prospects in the fields of photoelectricity, photovoltaic devices and the like.
Drawings
FIG. 1 shows CsPbI in example 1 of the present invention3/CaF2Yb, Er composite nano material and pure CsPbI3Quantum dots and pure CaF2X-ray powder diffraction contrast diagram of Yb, Er nanocrystals. The instrument model is MiniFlex2, Rigaku, and the radiation wavelength of the copper target is 0.154187 nm.
FIG. 2 shows CaF in example 1 of the present invention2Transmission electron microscope images of Yb, Er nanocrystalline with different resolutions. The instrument model is TECNAI G2F20, and the manufacturer is FEI.
FIG. 3 shows CsPbI in example 1 of the present invention3/CaF2Transmission electron microscope images of Yb and Er composite nano-materials with different resolutions. The instrument model is TECNAI G2F20, and the manufacturer is FEI.
FIG. 4 shows CsPbI in example 1 of the present invention3/CaF2Yb, Er composite nano material and pure CaF2Yb, Er nanocrystalline and pure CsPbI3Quantum dots and CaF2Yb, Er nanocrystals and CsPbI3An up-conversion emission spectrogram of the quantum dot physical mixed material under the excitation of a low-power density 980nm continuous semiconductor laser. The instrument model is FLS980, and the obstetrician is Edinburgh.
FIG. 5 shows CsPbI in example 1 of the present invention3/CaF2Yb, Er composite nano material and pure CaF2Yb and Er nanocrystals are subjected to up-conversion fluorescence lifetime spectrogram under 980nm laser excitation. The instrument model is FSP920-C, and the obstetrician is Edinburgh.
FIG. 6 shows CsPbI in example 1 of the present invention3/CaF2Yb, Er composite nano material, pure CsPbI3Quantum dots and CaF2Yb, Er nanocrystals and CsPbI3The quantum dot physical mixed material is subjected to down-conversion emission spectrogram under 365nm ultraviolet light excitation. The model of the instrument is FLS980, and the manufacturer is Edinburgh, the excitation light source is a xenon lamp.
FIG. 7 shows CsPbI in example 1 of the present invention3/CaF2Yb, Er composite nano material, pure CsPbI3Quantum dots and CaF2Yb, Er nanocrystals and CsPbI3And (3) converting the absolute fluorescence quantum yield histogram of the quantum dot physical mixed material under the excitation of 365nm ultraviolet light. The instrument model is FLS980, the obstetrician is Edinburgh, and the excitation light source is a xenon lamp.
FIG. 8 shows CsPbI in example 1 of the present invention3/CaF2Yb, Er composite nano material, pure CsPbI3Quantum dots and CaF2Yb, Er nanocrystals and CsPbI3The quantum dot physical mixed material converts fluorescence contrast photos under 365nm ultraviolet light excitation along with the increase of days of exposure in air. The instrument model is D7000 and the manufacturer is Nikon.
FIG. 9 shows CsPbI in example 1 of the present invention3/CaF2Yb, Er composite nano material, pure CsPbI3Quantum dots and CaF2Yb, Er nanocrystals and CsPbI3And (3) a down-conversion fluorescence thermal cycling stability curve of the quantum dot physical mixed material under the excitation of 365nm ultraviolet light. The instrument model is FLS980, the obstetrician is Edinburgh, and the excitation light source is a xenon lamp.
FIG. 10 shows CsPbCl in example 2 of the present invention3/CaF2Yb, Tm composite nano material, pure CaF2Yb, Tm nanocrystals and CaF2Yb, Tm nanocrystals and CsPbCl3An up-conversion emission spectrogram of the quantum dot physical mixed material under the excitation of a low-power density 980nm continuous semiconductor laser. The instrument model is FLS980, and the obstetrician is Edinburgh.
FIG. 11 shows CsPbBr in example 3 of the present invention3/CaF2Yb, Tm composite nano material, pure CaF2Yb, Tm nanocrystals and CaF2Yb, Tm nanocrystals and CsPbBr3An up-conversion emission spectrogram of the quantum dot physical mixed material under the excitation of a low-power density 980nm continuous semiconductor laser. The instrument model is FLS980, and the obstetrician is Edinburgh.
Fig. 12 is a schematic diagram of the structure of the rare earth upconversion and perovskite quantum dot composite nanomaterial of the present invention and the upconversion luminescence of the perovskite quantum dots achieved by fluorescence resonance energy transfer between the upconversion nanocrystals in the composite nanomaterial and the perovskite quantum dots under excitation of a low-power density 980nm continuous semiconductor laser.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Comparative example 1
CsPbI3Preparation of
(1) 0.4g of cesium carbonate was weighed into a two-necked round-bottom flask at room temperature, 1.5mL of oleic acid and 15mL of octadecene were added as solvents, heated to 120 ℃ under an inert atmosphere, and the cesium carbonate solution was dissolved with stirring for 1 hour. And (3) heating to 150 ℃ so that cesium carbonate and oleic acid completely react to obtain a cesium oleate solution, and cooling to 120 ℃ for storage after 10 minutes. Weighing 0.188mmol of lead iodide into a double-neck round-bottom flask at room temperature, adding 1.5mL of oleic acid, 1.5mL of oleylamine and 15mL of octadecene as solvents, heating to 120 ℃ under an inert atmosphere, and stirring and dissolving the lead iodide solution for 2 hours. Heating the lead iodide solution to 150 ℃ under inert atmosphere, quickly injecting the cesium oleate solution, reacting for 40 seconds under a static state, quickly cooling the reaction solution to room temperature in an ice water bath, and centrifuging to obtain CsPbI3And (4) quantum dots.
The prepared 0.05 mmole CsPbI3Quantum dots and 0.01mmol cubic phase CaF2Physical mixing of Yb and Er nanocrystals to obtain CaF2Yb, Er nanocrystals and CsPbI3Quantum dot physical hybrid materials.
Comparative example 2
CsPbCl3Preparation of
(1) 0.4g of cesium carbonate was weighed into a two-necked round-bottom flask at room temperature, 1.5mL of oleic acid and 15mL of octadecene were added as solvents, heated to 120 ℃ under an inert atmosphere, and the cesium carbonate solution was dissolved with stirring for 1 hour. And (3) heating to 150 ℃ so that cesium carbonate and oleic acid completely react to obtain a cesium oleate solution, and cooling to 120 ℃ for storage after 10 minutes. Weighing 0.188mmol of lead chloride into a double-neck round-bottom flask at room temperature, adding 1.5mL of oleic acid, 1.5mL of oleylamine and 15mL of octadecene as solvents, heating to 120 ℃ under an inert atmosphere, and stirring and dissolving the lead chloride solution for 2 hours. Heating the lead chloride solution to 150 ℃ under inert atmosphere, quickly injecting the cesium oleate solution, reacting for 40 seconds in a static state, quickly cooling the reaction solution to room temperature in an ice water bath, and centrifuging to obtain CsPbCl3And (4) quantum dots.
The prepared 0.05 mmole CsPbCl3Quantum dots and 0.01mmol cubic phase CaF2Physical mixing of Yb and Tm nanocrystals to obtain CaF2Yb, Tm nanocrystals and CsPbCl3Quantum dot physical hybrid materials.
Comparative example 3
CsPbBr3Preparation of
(1) 0.4g of cesium carbonate was weighed into a two-necked round-bottom flask at room temperature, 1.5mL of oleic acid and 15mL of octadecene were added as solvents, heated to 120 ℃ under an inert atmosphere, and the cesium carbonate solution was dissolved with stirring for 1 hour. And (3) heating to 150 ℃ so that cesium carbonate and oleic acid completely react to obtain a cesium oleate solution, and cooling to 120 ℃ for storage after 10 minutes. Weighing 0.188mmol of lead bromide into a double-neck round-bottom flask at room temperature, adding 1.5mL of oleic acid, 1.5mL of oleylamine and 15mL of octadecene as solvents, heating to 120 ℃ under an inert atmosphere, and stirring and dissolving the lead bromide solution for 2 hours. Heating the lead bromide solution to 150 ℃ under inert atmosphere, quickly injecting the cesium oleate solution, reacting for 40 seconds in a static state, quickly cooling the reaction solution to room temperature in an ice water bath, and centrifuging to obtain CsPbBr3And (4) quantum dots.
The prepared 0.05 mmole CsPbBr3Quantum dots and 0.01mmol cubic phase CaF2Physical mixing of Yb and Tm nanocrystals to obtain CaF2Yb, Tm nanocrystals and CsPbBr3Quantum dot physical hybrid materials.
Example 1
CsPbI3/CaF2Preparation of Yb, Er composite nano material
(1) Weighing calcium acetate monohydrate, ytterbium acetate tetrahydrate and erbium acetate tetrahydrate (1 mmol in total, the molar ratio of each element is 0.815 calcium: 0.18 ytterbium: 0.005 erbium) at room temperature into a double-mouth round-bottom flask, adding 5mL of oleic acid and 15mL of octadecene as solvents, heating to 160 ℃ under an inert atmosphere, stirring and dissolving the acetate solution for half an hour, and cooling to room temperature; 2.5mmol ammonium fluoride and 2.5mmol sodium hydroxide were weighed into 10mL methanol at room temperature, the solution was added to the acetate solution described above, heated to 60 ℃ under an inert atmosphere and stirred for half an hour to drain off the methanol. Heating the reaction solution to 280 ℃ under inert atmosphere, reacting for half an hour, naturally cooling to room temperature, precipitating and washing to obtain cubic phase CaF2Yb, Er nanocrystals, having a size of about 4nm (see FIG. 2), were shown in FIG. 1 for their X-ray powder diffraction pattern.
(2) CaF at room temperature2Firstly, dispersing Yb and Er nanocrystals into a mixed solvent of 0.5mL of oleic acid and 5mL of octadecene, and ultrasonically oscillating for 5 minutes. Subjecting said CaF to2Injecting a Yb and Er nanocrystalline solution into a double-mouth round-bottom flask, heating to 180 ℃ under an inert atmosphere, stirring for dissolving for 10 minutes, and cooling to 120 ℃ for storage; 0.4g of cesium carbonate was weighed into a two-necked round-bottom flask at room temperature, 1.5mL of oleic acid and 15mL of octadecene were added as solvents, heated to 120 ℃ under an inert atmosphere, and the cesium carbonate solution was dissolved with stirring for 1 hour. And (3) heating to 150 ℃ so that cesium carbonate and oleic acid completely react to obtain a cesium oleate solution, and cooling to 120 ℃ for storage after 10 minutes. Weighing 0.188mmol of lead iodide into a double-neck round-bottom flask at room temperature, adding 1mL of oleic acid, 1.5mL of oleylamine and 10mL of octadecene as a solvent, heating to 120 ℃ under an inert atmosphere, and stirring and dissolving the lead iodide solution for 1 hour. Subjecting said CaF to2The Yb and Er nanocrystalline solution is added into the lead iodide solution drop by drop. Keeping the mixed solution at 120 ℃, slowly stirring for 1 hour under the inert atmosphere, heating to 150 ℃, quickly injecting the cesium oleate solution, and reacting for 40 seconds in a static stateThen, the reaction solution was rapidly cooled to room temperature in an ice-water bath, and centrifuged to obtain CsPbI3/CaF2The Yb and Er composite nano material has good dispersibility, uniform appearance and a size of about 25nm (shown in figure 3), and an X-ray powder diffraction pattern of the material is shown in figure 1.
The prepared CsPbI3/CaF2CsPbI in Yb, Er composite nano material3With CaF2Yb and Er in the molar ratio of 5 to 1, and the molar ratio of Yb to Er is the charge ratio.
As shown in FIG. 1, CsPbI3/CaF2Yb, Er composite nano material with pure CaF2Yb, Er nanocrystalline and pure CsPbI3And (3) an X-ray powder diffraction characteristic peak of the quantum dot.
As shown in FIG. 3, CaF2Embedding Yb, Er nanocrystalline into CsPbI3In a quantum dot matrix. By taking the interplanar spacing of the small squares and dark particles in the graph and comparing the two cubic PDF cards, it can be determined that calcium fluoride nanocrystals are in the white circles in the graph (b) in FIG. 3, and the dispersed substrate is CsPbI3Quantum dots, and thus can further illustrate that the combination of these two materials is atomic scale.
As shown in FIG. 4, CsPbI is excited under a low power density 980nm continuous semiconductor laser3/CaF2The Yb and Er composite nano material shows red light (680-760nm) up-conversion emission and pure CsPbI3The wavelength bands of the down-conversion emission of the quantum dots are consistent (refer to the b curve in fig. 6 in particular). While a low-power density 980nm continuous semiconductor laser cannot excite pure CsPbI3Quantum dots and CaF2Yb, Er nanocrystals and CsPbI3Up-conversion emission of quantum dot physical hybrid materials.
As shown in FIG. 5, pure CaF2Er in Yb, Er nanocrystals3+Is/are as follows4F9/2Effective upconversion lifetime of energy states (τ)2) 0.48ms, approximately CsPbI3/CaF2Effective upconversion lifetime (tau) of this energy state in Yb, Er composite nanomaterials11.26 μ s). The fluorescence resonance energy transfer efficiency is as high as 99.7%.
As shown in fig. 6, under the same test conditions,CsPbI3/CaF2the integrated intensity of the down-converted emission spectra of Yb, Er composite nanomaterials is about pure CsPbI respectively3Quantum dots and CaF2Yb, Er nanocrystals and CsPbI 32 times and 14.8 times of the quantum dot physical mixed material.
As shown in FIG. 7, CsPbI was tested under the same test conditions3/CaF2Yb, Er composite nano material, pure CsPbI3Quantum dots and CaF2Yb, Er nanocrystals and CsPbI3The down-conversion absolute fluorescence quantum yield of the quantum dot physical mixed material is 45.9 +/-7.2%, 34.4 +/-12.2% and 2.1 +/-1.3%, respectively.
As shown in FIG. 8, the samples were exposed to air, CaF2Yb, Er nanocrystals and CsPbI3CsPbI is caused by instability of quantum dot physical mixed material within 2 hours3The quantum dots are converted into a non-luminous yellow orthogonal phase; pure CsPbI3The quantum dots are converted to a non-luminescent yellow orthorhombic phase in about 4 days; and CsPbI3/CaF2The Yb and Er composite nano material still emits bright down-conversion fluorescence after 12 days.
As shown in FIG. 9, CsPbI is subjected to a thermal cycle of increasing temperature from room temperature to 410K and then decreasing temperature3/CaF2The Yb and Er composite nano material still maintains the fluorescence intensity converted at room temperature accounting for 47 percent of the initial intensity. And CaF2Yb, Er nanocrystals and CsPbI3Quantum dot physical mixed material and pure CsPbI3After undergoing a thermal cycling process, quantum dots are barely detectable of their down-conversion emission at room temperature.
Example 2
CsPbCl3/CaF2Preparation of Yb, Tm composite nano material
(1) Weighing calcium acetate monohydrate, ytterbium acetate tetrahydrate and thulium acetate tetrahydrate (1 mmol in total, the molar ratio of each element is 0.815 calcium: 0.18 ytterbium: 0.005 thulium) at room temperature into a double-mouth round-bottom flask, adding 5mL of oleic acid and 15mL of octadecene as solvents, heating to 160 ℃ under an inert atmosphere, stirring and dissolving the acetate solution for half an hour, and cooling to room temperature; 2.5mmol ammonium fluoride and 2.5mmol sodium hydroxide were weighed at room temperatureAdded to 10mL of methanol, the solution was added to the acetate solution described above, heated to 60 ℃ under an inert atmosphere and stirred for half an hour to drain off the methanol. Heating the reaction solution to 280 ℃ under inert atmosphere, reacting for half an hour, naturally cooling to room temperature, precipitating and washing to obtain cubic phase CaF2Yb, Tm nanocrystals, about 4nm in size.
(2) CaF at room temperature2The Yb and Tm nano crystal is firstly dispersed in a mixed solvent of 0.5mL of oleic acid and 5mL of octadecene and is subjected to ultrasonic oscillation for 5 minutes. Subjecting said CaF to2Injecting Yb and Tm nanocrystalline solution into a double-mouth round-bottom flask, heating to 180 ℃ under inert atmosphere, stirring for dissolving for 10 minutes, and cooling to 120 ℃ for storage; 0.4g of cesium carbonate was weighed into a two-necked round-bottom flask at room temperature, 1.5mL of oleic acid and 15mL of octadecene were added as solvents, heated to 120 ℃ under an inert atmosphere, and the cesium carbonate solution was dissolved with stirring for 1 hour. And (3) heating to 150 ℃ so that cesium carbonate and oleic acid completely react to obtain a cesium oleate solution, and cooling to 120 ℃ for storage after 10 minutes. Weighing 0.188mmol of lead chloride into a double-neck round-bottom flask at room temperature, adding 1mL of oleic acid, 1.5mL of oleylamine and 10mL of octadecene as solvents, heating to 120 ℃ under an inert atmosphere, and stirring and dissolving the lead chloride solution for 1 hour. Subjecting said CaF to2The Yb, Tm nanocrystalline solution is added dropwise to the lead chloride solution. Keeping the mixed solution at 120 ℃, slowly stirring for 1 hour under the inert atmosphere, heating to 150 ℃, quickly injecting the cesium oleate solution, reacting for 40 seconds in a static state, quickly cooling the reaction solution to room temperature in an ice water bath, and centrifuging to obtain CsPbCl3/CaF2The Yb and Tm composite nano material has good dispersibility, uniform appearance and about 25nm size.
Prepared CsPbCl3/CaF2CsPbCl in Yb, Tm composite nano material3With CaF2Yb and Tm are in a molar ratio of 5:1, and the molar ratio of Yb to Tm is the feed ratio.
As shown in FIG. 10, CsPbCl was excited under a low power density 980nm continuous semiconductor laser3/CaF2The Yb, Tm composite nano material shows blue light (400-3The wavelength bands of the down-conversion emission of the quantum dots are consistent. But of low powerCaF (stimulated fluorescence) incapable of being excited by 980nm continuous semiconductor laser2Yb, Tm nanocrystals and CsPbCl3Up-conversion emission of quantum dot physical hybrid materials.
Example 3
CsPbBr3/CaF2Preparation of Yb, Tm composite nano material
(1) Weighing calcium acetate monohydrate, ytterbium acetate tetrahydrate and thulium acetate tetrahydrate (1 mmol in total, the molar ratio of each element is 0.815 calcium: 0.18 ytterbium: 0.005 thulium) at room temperature into a double-mouth round-bottom flask, adding 5mL of oleic acid and 15mL of octadecene as solvents, heating to 160 ℃ under an inert atmosphere, stirring and dissolving the acetate solution for half an hour, and cooling to room temperature; 2.5mmol ammonium fluoride and 2.5mmol sodium hydroxide were weighed into 10mL methanol at room temperature, the solution was added to the acetate solution described above, heated to 60 ℃ under an inert atmosphere and stirred for half an hour to drain off the methanol. Heating the reaction solution to 280 ℃ under inert atmosphere, reacting for half an hour, naturally cooling to room temperature, precipitating and washing to obtain cubic phase CaF2Yb, Tm nanocrystals, about 4nm in size.
(2) CaF at room temperature2The Yb and Tm nano crystal is firstly dispersed in a mixed solvent of 0.5mL of oleic acid and 5mL of octadecene and is subjected to ultrasonic oscillation for 5 minutes. Subjecting said CaF to2Injecting Yb and Tm nanocrystalline solution into a double-mouth round-bottom flask, heating to 180 ℃ under inert atmosphere, stirring for dissolving for 10 minutes, and cooling to 120 ℃ for storage; 0.4g of cesium carbonate was weighed into a two-necked round-bottom flask at room temperature, 1.5mL of oleic acid and 15mL of octadecene were added as solvents, heated to 120 ℃ under an inert atmosphere, and the cesium carbonate solution was dissolved with stirring for 1 hour. And (3) heating to 150 ℃ so that cesium carbonate and oleic acid completely react to obtain a cesium oleate solution, and cooling to 120 ℃ for storage after 10 minutes. Weighing 0.188mmol of lead bromide into a double-neck round-bottom flask at room temperature, adding 1mL of oleic acid, 1.5mL of oleylamine and 10mL of octadecene as solvents, heating to 120 ℃ under an inert atmosphere, and stirring and dissolving the lead bromide solution for 1 hour. Subjecting said CaF to2The Yb, Tm nanocrystalline solution is added dropwise to the lead bromide solution. Keeping the mixed solution at 120 ℃, slowly stirring for 1 hour under an inert atmosphere, heating to 150 ℃, quickly injecting the cesium oleate solution,after reacting for 40 seconds in a static state, the reaction solution is rapidly cooled to room temperature in an ice-water bath, and CsPbBr is obtained by centrifugation3/CaF2The Yb and Tm composite nano material has good dispersibility, uniform appearance and about 25nm size.
Prepared CsPbBr3/CaF2CsPbCl in Yb, Tm composite nano material3With CaF2Yb and Tm are in a molar ratio of 5:1, and the molar ratio of Yb to Tm is the feed ratio.
As shown in FIG. 11, CsPbBr was excited under a low power density of 980nm continuous semiconductor laser3/CaF2The Yb, Tm composite nano material shows green light (490-560nm) up-conversion emission and pure CsPbBr3The wavelength bands of the down-conversion emission of the quantum dots are consistent. The low-power 980nm continuous semiconductor laser cannot excite CaF2Yb, Tm nanocrystals and CsPbBr3Up-conversion emission of quantum dot physical hybrid materials.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (59)
1. A rare earth up-conversion and perovskite quantum dot composite nanomaterial, wherein the composite nanomaterial comprises up-conversion nanoparticles and perovskite quantum dots, the up-conversion nanoparticles having a chemical formula of: CaF2Ln, wherein Ln is Yb3+/Er3+And Yb3+/Tm3+(ii) a The perovskite quantum dot is CsPbX3The quantum dots are characterized in that X is selected from one of Cl, Br and I; the up-conversion nano particles and the perovskite quantum dots are combined at an atomic scale, and the up-conversion nano particles are embedded in the perovskite quantum dots and are bonded and connected through chemical bonds.
2. The composite nanomaterial of claim 1, wherein the rare earth up-conversion and perovskite quantum dot composite nanomaterial has a chemical formula of CsPbX3/CaF2:Ln。
3. The composite nanomaterial of claim 2, wherein the rare earth up-conversion and perovskite quantum dot composite nanomaterial has a chemical formula of CsPbCl3/CaF2:Yb,Tm、CsPbBr3/CaF2:Yb,Tm、CsPbI3/CaF2:Yb,Tm、CsPbCl3/CaF2:Yb,Er、CsPbBr3/CaF2Yb, Er and CsPbI3/CaF2:Yb,Er。
4. The composite nanomaterial of claim 1, wherein the molar ratio of Yb to Tm is (5-40): (0.5-2); the molar ratio of Yb to Er is (5-40) to (0.5-2).
5. The composite nanomaterial of claim 4, wherein the molar ratio of Yb to Tm is (9-36): (0.8-1.2); the molar ratio of Yb to Er is (9-36) to (0.8-1.2).
6. The composite nanomaterial of claim 5, wherein the Yb and Tm are in a molar ratio of 36: 1; the molar ratio of Yb to Er is 36: 1.
7. The composite nanomaterial of claim 1, wherein the crystal system of the upconverting nanoparticle is a cubic phase calcium fluoride nanocrystal structure.
8. The composite nanomaterial of claim 1, wherein the crystal system of the perovskite quantum dots is a cubic phase structure.
9. The composite nanomaterial according to claim 1, wherein the particle size of the upconversion nanoparticle is 1 to 10 nm.
10. The composite nanomaterial according to claim 9, wherein the size of the upconversion nanoparticle is 2 to 5 nm.
11. The composite nanomaterial according to claim 10, wherein the size of the upconversion nanoparticle is 3 to 4 nm.
12. The composite nanomaterial of claim 1, wherein the CsPbX is3The particle size of the quantum dots is 5-50 nm.
13. The composite nanomaterial of claim 12, wherein the CsPbX is3The particle size of the quantum dots is 10-40 nm.
14. The composite nanomaterial of claim 13, wherein the CsPbX is3The particle size of the quantum dots is 20-30 nm.
15. The composite nanomaterial according to claim 1, wherein in the rare earth up-conversion and perovskite quantum dot composite nanomaterial, the molar ratio of perovskite quantum dots to up-conversion nanoparticles is (3-6): (0.5-2).
16. The composite nanomaterial of claim 15, wherein in the rare earth up-conversion and perovskite quantum dot composite nanomaterial, the molar ratio of perovskite quantum dots to up-conversion nanoparticles is (4.5-5.5): (0.5-1.5).
17. The composite nanomaterial according to claim 1, wherein the particle size of the rare earth up-conversion and perovskite quantum dot composite nanomaterial is 1 to 50 nm.
18. The composite nanomaterial of claim 17, wherein the particle size of the rare earth up-conversion and perovskite quantum dot composite nanomaterial is 10-50 nm.
19. The composite nanomaterial of claim 18, wherein the particle size of the rare earth up-conversion and perovskite quantum dot composite nanomaterial is 20-40 nm.
20. A method of producing a composite nanomaterial according to any of claims 1 to 19, comprising the steps of:
(1) preparing an upconversion nanoparticle having the formula: CaF2Ln, wherein Ln is Yb3+/Er3+And Yb3+/Tm3+；
(2) Preparing the rare earth up-conversion nano particles and the perovskite quantum dot composite nano material; the step (2) comprises the following steps:
(2-1) mixing and reacting cesium carbonate, oleic acid and octadecene to obtain a cesium oleate solution;
(2-2) mixing lead halide, oleic acid, oleylamine and octadecene to obtain a lead halide solution;
(2-3) mixing and reacting the up-conversion nano particles, the cesium oleate solution and the lead halide solution to prepare the composite nano material.
21. The preparation method of claim 20, wherein the upconversion nanoparticle is prepared by a method comprising:
(1-1) mixing a calcium source and an Ln source and dissolving into oleic acid and octadecene to obtain a mixed system A, wherein Ln is Yb3+/Er3+And Yb3+/Tm3+；
(1-2) mixing ammonium fluoride, sodium hydroxide and methanol to obtain a mixed system B;
(1-3) mixing the mixed system A obtained in the step (1-1) with the mixed system B obtained in the step (1-2), and reacting to prepare the up-conversion nanoparticles.
22. The production method according to claim 21, wherein in the step (1-1), the calcium source is calcium acetate; the Ln source is ytterbium acetate and erbium acetate or ytterbium acetate and thulium acetate.
23. The method according to claim 21, wherein the molar ratio of the calcium source to the Ln source in step (1-1) is (0.5-0.95): (0.046-0.41).
24. The method according to claim 23, wherein the molar ratio of the calcium source to the Ln source in the step (1-1) is (0.78-0.89): (0.1004-0.2006).
25. The method according to claim 22, wherein the molar ratio of calcium acetate, ytterbium acetate, erbium acetate or thulium acetate is (0.5-0.95): (0.045-0.4): (0.001-0.01).
26. The method of claim 25, wherein the molar ratio of calcium acetate, ytterbium acetate, erbium acetate or thulium acetate is (0.78-0.89): (0.1-0.2): (0.004-0.006).
27. The method according to claim 21, wherein the volume ratio of oleic acid to octadecene in the step (1-1) is (1-10): (10-20).
28. The method according to claim 27, wherein the volume ratio of oleic acid to octadecene in the step (1-1) is (3-6): (14-16).
29. The method according to claim 21, wherein in the step (1-1), the molar volume ratio of the calcium source to the oleic acid in the mixed system A is (0.5 to 0.95mmol): 1 to 10 ml.
30. The method according to claim 29, wherein in the step (1-1), the molar volume ratio of the calcium source to the oleic acid in the mixed system A is (0.78-0.89 mmol): 3-6 ml.
31. The method according to claim 21, wherein the mixing and dissolving in the step (1-1) are carried out by heating to 140 to 180 ℃ under an inert atmosphere and stirring for 0.2 to 1 hour.
32. The method according to claim 21, wherein in the step (1-2), the molar ratio of ammonium fluoride to sodium hydroxide is (1-5) to (1-5), and the molar volume ratio of ammonium fluoride to methanol is 0.1-0.5 mmol/mL.
33. The method according to claim 32, wherein in the step (1-2), the molar ratio of ammonium fluoride to sodium hydroxide is (2-3) to (2-3), and the molar volume ratio of ammonium fluoride to methanol is 0.2-0.3 mmol/mL.
34. The production method according to claim 21, wherein in the step (1-3), the volume ratio of mixed system a to mixed system B is (1-5): 1.
35. the production method according to claim 34, wherein in the step (1-3), the volume ratio of the mixed system a to the mixed system B is (2-3): 1.
36. the method according to claim 21, wherein the reaction is carried out in step (1-3) by heating to 260 to 300 ℃ under an inert atmosphere for 0.2 to 1 hour.
37. The method according to claim 20, wherein the mixing in the step (2-1) is performed under an inert atmosphere and with stirring, and the mixing temperature is 100 to 130 ℃ and the mixing time is 0.8 to 1.2 hours.
38. The preparation method according to claim 20, wherein in the step (2-1), the reaction is carried out under an inert atmosphere and under stirring, the temperature of the reaction is 140 to 160 ℃, and the time of the reaction is 8 to 15 minutes.
39. The preparation method according to claim 20, wherein in the step (2-1), the mass-to-volume ratio of cesium carbonate to oleic acid is (0.3-0.7 g): 1-2 mL.
40. The preparation method according to claim 39, wherein in the step (2-1), the mass-to-volume ratio of cesium carbonate to oleic acid is (0.4-0.5 g): (1.5-1.8 mL).
41. The method according to claim 20, wherein in the step (2-1), the volume ratio of oleic acid to octadecene is (1-5): (10-20).
42. The method according to claim 41, wherein the volume ratio of oleic acid to octadecene in the step (2-1) is (1-2): (14-16).
43. The method according to claim 20, wherein the mixing in the step (2-2) is performed under an inert atmosphere and with stirring, and the mixing temperature is 100 to 130 ℃ and the mixing time is 0.8 to 1.2 hours.
44. The production method according to claim 20, wherein in the step (2-2), the lead halide is at least one selected from the group consisting of lead chloride, lead bromide and lead iodide.
45. The production method according to claim 20, wherein in the step (2-2), the molar volume ratio of the lead halide to the oleic acid is (0.15 to 0.2mmol): 0.5 to 2 ml.
46. The production method according to claim 45, wherein in the step (2-2), the molar volume ratio of the lead halide to the oleic acid is (0.18 to 0.19mmol): 0.5 to 1.5 ml.
47. The method according to claim 20, wherein the volume ratio of the oleic acid, the oleylamine and the octadecene in the step (2-2) is (0.5-2): (1-5): (5-15).
48. The method according to claim 47, wherein in the step (2-2), the volume ratio of the oleic acid, the oleylamine and the octadecene is (0.5-1.5): (1-2): (8-12).
49. The method according to claim 20, wherein the mixing in the step (2-3) is performed under an inert atmosphere and with stirring, and the mixing temperature is 100 to 130 ℃ and the mixing time is 0.8 to 1.2 hours.
50. The preparation method according to claim 20, wherein in the step (2-3), the mixing is carried out by mixing the upconversion nanoparticles with a lead halide solution, then heating, adding a cesium oleate solution, and reacting in a static state.
51. The preparation method of claim 20, wherein in the step (2-3), the upconversion nanoparticles are directly mixed with the lead halide solution, or are prepared into an upconversion nanoparticle dispersion solution and then mixed with the lead halide solution.
52. The method for preparing a pharmaceutical composition according to claim 51, wherein in the step (2-3), the formulation process is: dispersing the upconversion nanoparticles in oleic acid and octadecene to obtain a dispersion liquid of the upconversion nanoparticles; the dispersion is carried out under the conditions of inert atmosphere and stirring, the dispersion temperature is 160-200 ℃, and the dispersion time is 5-15 minutes.
53. The production method according to claim 20, wherein in the step (2-3), the volume ratio of oleic acid to octadecene is (0.2-1): (2-10); the mol volume ratio of the upconversion nanoparticles to the oleic acid is (0.15-1.5 mmol): 0.5-2 ml.
54. The production method according to claim 20, wherein in the step (2-3), the volume ratio of oleic acid to octadecene is (0.4-0.6): (4-6); the mol volume ratio of the upconversion nanoparticles to the oleic acid is (0.25-0.75 mmol): 0.5-1.5 ml.
55. The method according to claim 20, wherein in the step (2-3), the reaction is carried out under an inert atmosphere, the temperature of the reaction is 140 to 160 ℃, and the time of the reaction is 30 to 50 seconds.
56. The preparation method according to claim 20, wherein in the step (2-3), after the reaction is completed, the reaction solution is rapidly cooled to room temperature in an ice-water bath, and then is subjected to centrifugal separation to obtain the composite nanomaterial.
57. The preparation method according to claim 20, wherein in the step (2-3), the mass-to-volume ratio of the up-conversion nanoparticles, the cesium oleate solution and the lead halide solution is (0.02-0.03 g): (0.35-0.45 mL): (12-13 mL).
58. The rare earth up-conversion and perovskite quantum dot composite nanomaterial prepared by the method for preparing a rare earth up-conversion and perovskite quantum dot composite nanomaterial of any one of claims 20 to 57.
59. Use of the rare earth up-conversion and perovskite quantum dot composite nanomaterial of any one of claims 1 to 19, 58 as an up-conversion and down-conversion dual mode luminescent material; or in the field of photovoltaic and photovoltaic devices.
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